Consuming two major greenhouse gases, carbon dioxide (CO2) and methane (CH4), to produce synthesis gas, which is a mixture of carbon monoxide (CO) and hydrogen (H2), CO2 reforming of CH4 shows significant environmental and economic benefits. However, the process has not found wide industrial application due to severe catalyst deactivation, basically caused by carbon formation. Therefore, it is of great interest to develop stable catalysts without severe deactivation. This work is primarily focused on the development of novel nickel-based catalysts to achieve stable operation for CO2 reforming of CH4.<p> Following Dowdens strategy of catalyst design, a series of nickel-based catalysts are designed with a general formula: Ni-Me/AlMgOx (Me = Co, Cu, Fe, or Mn). The designed catalysts are prepared using co-precipitation method and tested for CO2 reforming of CH4. Catalyst screening showed that the Ni-Co/AlMgOx catalyst has superior performance in terms of activity and stability to other Ni-Me/AlMgOx (Me = Cu, Fe, or Mn) catalysts. A 2000 h long-term deactivation test has shown that the Ni-Co/AlMgOx has high activity and excellent stability for CO2 reforming of CH4.<p> Further investigation on the Ni-Co/AlMgOx catalysts shows that adjusting Ni/Co ratio and Ni-Co loading can significantly affect the catalyst performance. Carbon free operation for CO2 reforming of CH4 can be achieved on the catalysts with a Ni/Co close to 1 and Ni-Co overall loading between 4-10 %. In addition, calcination temperature shows important impacts on the performance of Ni-Co/AlMgOx catalysts. A calcination temperature range of 700-900 oC is recommended.<p> The Ni-Co/AlMgOx catalysts are characterized using various techniques such as ICP-MS, BET, CO-chemiosorption, XRD, TPR, TG/DTA, TEM, and XPS. It has been found that the high activity and excellent stability of Ni-Co/AlMgOx catalysts can be ascribed to its high surface area, high metal disperation, small particle size, strong metal-support interaction, and synergy between Ni and Co.<p> Kinetic studies have shown that the CH4 decomposition and CO2 activation could be the rate-determining steps. Both Power-Law and Langmuir-Hinshelwood kinetic models can fit the experiment data with satisfactory results.

The reforming of CH4 reaction with CO2 was studied over supported catalysts. From this study, we have recognized that the catalytic behavior of the copper catalysts were affected by many factors such as the reaction temperature, the categories of precursors of active metals, the additives, and the supports of the catalysts. In this study, it was found that the catalysts having carbon depositions not only performed higher activities but also became more stable. TPO results have shown that three types of carbonaceous species, C£\, C£] and C£^, were found to exist on the supported copper catalyst during CH4-CO2 reforming reaction. The mechanism of the carbon deposition was also investigated, and we propose a model to explain this process. The effects of various additives on the performance of the catalysts were also explored. We found that the Cu/Ni/SiO2 bimetallic catalysts exhibited high activities regardless of the ratio of Cu/Ni. These catalysts exhibited higher activity and stability than the monometallic catalyst at 800¢J. The deactivation rates of these catalysts were only about 0.15- 0.31% h-1 (after more than 20 hours on stream). Therefore, the Cu/Ni/SiO2 bimetallic catalysts are preferable for the carbon dioxide reforming of methane.

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The development of an auxiliary power unit (APU) capable of providing climate control and electricity in long haul trucks is of significant interest due to the expected economic and environmental benefits. A potentially efficient and environmentally friendly APU design is one based on the use of an autothermal fuel reformer that converts on-board truck fuel to a hydrogen rich gas that directly fuels a solid oxide fuel cell unit. To assist in the development of such a unit a numerical study of the autothermal reforming of iso-octane in a compact tubular reactor has been undertaken. This was done to determine the reactor performance and the factors that potentially influence its performance. Variations in the wall thermal conductivity, the catalyst thermal conductivity, the catalyst porosity, the conditions of the inlet reactant gas, and the effectiveness factor of the chemical reaction mechanism have been studied to determine their effects on the performance of the reformer. It has been found that higher thermal conductivities of the outer wall and in the catalyst region gave increased dry hydrogen yield and fuel conversion. The study of the effects of inlet species concentration ratios indicated that maximum hydrogen yield was obtained with an oxygen-to-fuel ratio between 1.0 and 1.15 and a steam-to-fuel ratio of approximately 3.0. Results obtained with various inlet species temperatures and bed porosities showed only small changes in the reformer performance. While the results obtained here do provide useful information about the performance of the autothermal reformer, the model used has been re-assessed and it is recommended that an improved model be used in future work. In particular, the assumed effectiveness factors for all of the chemical reactions occurring in the catalyst region need to be improved. This was highlighted by the fact that a brief study indicated a very strong dependence of the reformer product gas composition on the effectiveness factor. This indicates that while the present model is able to predict trends in the reformer performance, it is limited in its accuracy due to the fact that the effectiveness factor used is only approximately known. / Thesis (Master, Mechanical and Materials Engineering) -- Queen's University, 2007-08-31 13:22:27.466

Utilisation of natural gas (mainly methane, CH[subscript]4), a clean and abundant resource, is of great importance. Conventional method, steam reforming, though still dominant, requires a considerately high capital investment and an intensive energy input. Reforming natural gas by partial oxidation, potentially one of the most attractive alternatives, has been investigated vigorously for decades, mainly focusing on looking for suitable catalyst and understanding of the mechanisms of methane partial oxidation. This work focuses on the feasibility of methane partial oxidation reforming from gas phase reaction under fuel-rich conditions.Firstly, a detailed thermodynamic analysis has been conducted, which covers a broad range of operation conditions of temperature up to 2073 K, pressure up to 100 atm and initial O(subscript)2/CH(subscript)4 ratio of 0 to 2.5. It has been found that high syn-gas (H(subscript)2 and CO) yields can be achieved when the temperature is above 1073 K and the initial O(subscript)2/CH(subscript)4 ratio close to 0.5. High pressure is not favoured. However, high temperatures can suppress the effect of high pressures.Carbon deposition, a crucially important factor in methane partial oxidation, is mainly examined by means of thermodynamic analysis. Solid carbon was identified the major carbon deposition form, which could severely happen if the initial O(subscript)2/CH(subscript)4 ratio is less than 0.5. This feature was also indirectly proven during the experimental tests.Secondly, a series of CHEMKIN simulations were performed using various CH(subscript)4 oxidation reaction mechanisms. The general trend of the CH(subscript)4 partial oxidation reforming was revealed by simulations using the GRI, NIST and Konnov mechanisms. A new concept characterising CH(subscript)4 partial oxidation was conceived. i.e., a fast oxidation zone and a slow conversion ++ / zone, the reaction is under chemical control that requests high operating temperatures, and the reaction can be accelerated by using relatively high initial 0(subscript)2/CH(subscript)4 ratios.Experimental tests were performed to verify the findings obtained in thermodynamic and kinetic studies, and to identify appropriate reaction schemes for further analysis. Prediction from the NIST mechanisms has shown to be in good agreement with experimental observation when the temperature is less than 1273 K. For higher temperatures the NIST under-predicts the H(subscript)2 yield caused by the lack of carbon formation mechanisms. Two other mechanisms (Konnov and GRI) predicted similar trends but the reaction predicted commenced earlier. Therefore, the NIST was identified to be the best.NO(subscript)x catalytic effect on CH4 oxidation at fuel-rich conditions was confirmed experimentally. However, this effect only exists where the oxygen is available. Therefore, employing NO(subscript)x cannot help the CH(subscript)4 partial oxidation in the second reaction zone. Solely relying on NO(subscript)x to speed up the process or lower the operating temperature is not possible. However, employing NO(subscript)x to initiate the reaction at lower temperatures is viable. The possibility of taking the advantage of NOx catalytic effect for direct synthesis of CH3OH (methanol) has been shown feasible and, more attractively, the operating temperatures required are much lower than that for syn-gas production.Among three reaction schemes, i.e., the Glarborg, Bromly and Dagaut, which are able to account for the NO(subscript)x catalytic effect, the Glarborg mechanism proved to be the best in reproducing experimental measurements for syn-gas production tests. However, none available mechanisms can predict similar magnitude of the direct synthesis of CH(subscript)3OH. To understand the mechanisms ++ / of NO(subscript)x catalytic effect, a reaction scheme, Partial Oxidation Mechanisms (POM), has been composed successfully adding five additional reactions into the NIST. The POM can reveal the major catalytic reaction pathways and it is suitable for CH(subscript)4 partial oxidations both with and without NO(subscript)x addition.Finally, a series of simulations were conducted to conservatively estimate the feasibility of CH(subscript)4 partial oxidation using POM. High syn-gas yield is achievable within a reasonable residence time using adiabatic reactor. The variables significantly affecting the syn-gas yield, are preheating temperature, operating pressure, inert dilution, initial ratio of O(subscript)2/CH(subscript)4 and residence time. If NO(subscript)x is used as a catalyst, the preheating temperature can be further reduced.

Uma das principais aplicações do metano é a produção de gás de síntese, mistura de hidrogênio e monóxido de carbono. Três processos podem levar à formação de gás de síntese a partir do metano: reforma a vapor, reforma com CO2 e oxidação parcial. Vários catalisadores de metais não-preciosos foram estudados para os processos de reforma, embora a deposição de carbono ou a sinterização do metal sempre esteja presente. Catalisadores obtidos de precursores do tipo hidrotalcita têm se mostrado resistentes à coqueificação nas reações de reforma a vapor do metano, podendo ser aplicados ao processo combinado de reforma e oxidação parcial de metano para obtenção de gás de síntese, com potencial para minimizar as dificuldades inerentes aos processos: altas temperaturas e desativação do catalisador. Catalisadores de níquel e de cobalto, obtidos a partir de precursores do tipo hidrotalcita, com a adição de cério e de lantânio como promotores, foram preparados, caracterizados e aplicados em testes catalíticos nas reações de reforma a vapor, oxidação parcial e reforma oxidativa do metano, com o intuito de avaliar a atividade e estabilidade destes catalisadores e o efeito dos promotores. Os catalisadores não-promovidos foram obtidos por três métodos: método tradicional, método da co-precipitação com quelato, e troca-ânionica. A adição de promotores foi feita por troca-aniônica. Os compostos foram caracterizados por Energia dispersiva de Raios-X , Área Superficial Específica Total, Análise Termogravimétrica, Difração de Raios-X, Espectroscopia de Absorção na região do Infravermelho, Redução a Temperatura Programada, Espectroscopia Fotoeletrônica de Raios-X, Espectroscopia de Absorção de Raios-X e testes catalíticos com as reações de Reforma a vapor do metano, com razões molares de alimentação H2O:CH4= 4:1; 2:1 e 0,5:1, Oxidação Parcial do metano com razões molares de alimentação CH4:O2=2:1 e 4:1 e Reforma oxidativa do metano com razão molar de alimentação CH4:H2O:O2= 4:4:1. Os catalisadores mostraram-se ativos nas reações de reforma a vapor do metano, com exceção dos catalisadores de cobalto que não foram ativos para a razão de alimentação H2O:CH4= 4:1. A adição de promotores favoreceu a reação de deslocamento gás-água. Nas reações de oxidação parcial do metano, os catalisadores foram ativos para a razão de alimentação CH4:O2=4:1, com considerável redução na velocidade de formação de carbono para os catalisadores promovidos. Na reforma oxidativa do metano, o acoplamento levou a um favorecimento na seletividade para formação de CO2 e a uma maior velocidade de formação de carbono. / One of the most important applications of methane is the syngas production, a mixture of H2 and CO. Three processes can lead to syngas formation from methane: steam reforming, CO2 reforming and partial oxidation. Various non-noble metal catalysts were studied in these processes, although the carbon deposition or the metal sinterization is always observed. Catalysts prepared from hydrotalcite precursors have presented resistance to carbon deposition, and considering this aspect they could be applied to the combined process of methane reforming with partial oxidation to produce syngas, with potential to minimize the difficulties of the process: high temperatures and catalyst deactivation. In this work, nickel and cobalt catalysts, prepared from hydrotalcites and promoted with lanthanum and cerium, were prepared, characterized and tested in the reactions of steam reforming, partial oxidation and oxidative reforming of methane, with the goal of evaluating the activity and stability of these catalysts and the effect of promoter addition. The un-promoted catalysts were prepared through three methods: the traditional method, the method of co-precipitation with chelate and the anion-exchange method. The promoter addition was made through the anion-exchange method. The compounds were characterized by Energy Dispersive X-Ray Spectroscopy (EDX), Specific Surface Area, Thermo gravimetric Analysis, X-Ray Diffraction (XRD), Fourier Transformed Infrared Spectroscopy (FTIR), Temperature Programend Reduction (TPR), X-Ray Photoelectron Spectroscopy (XPS), X-Ray Absortion Spectroscopy (XAS) and catalytic tests using the folowing reactions of methane: steam reforming with molar ratio in feed of H2O:CH4= 4:1; 2:1 and 0,5:1, partial oxidation with molar ratio in feed of CH4:O2=2:1 e 4:1 and oxidative reforming with molar ratio in feed of CH4:H2O:O2= 4:4:1. All catalysts showed activity for methane steam reforming, except the cobalt catalysts, which did not present activity for the reaction with molar in feed of H2O:CH4= 4:1. The promoters addition favored the shift reaction. For the partial oxidation reactions, the catalysts presented activity for molar ratio in feed of CH4:O2=4:1, with pronounced reduction in the velocity of carbon formation for promoted catalysts. In the oxidative reforming, the coupling of the reactions lead to a favoring in the selectivity for CO2 but a higher velocity of carbon formation.\"

Steam reforming of methanol and hydrocarbon are currently the processes of choice to produce hydrogen. Due to the endothermic nature of these reactions, zones of low temperature are commonly found in reformers. These zones can potentially damage the reformer through thermal stresses. Moreover, the response time and size of a reformer are controlled by the heat available to the reaction. The objective of this thesis is to demonstrate the feasibility of using fiber Bragg gratings as an alternative solution for temperature monitoring in methanol and methane steam reformers. To meet this objective, a sensor array containing seven gratings is placed in a metal-plate test reformer. First, temperature monitoring during methanol steam reforming is conducted in 12 different sets of conditions. The resulting profile of the temperature change along the length of the catalyst captures the zones of low temperature caused by the endothermic nature of the reaction. Several small changes in the temperature profile caused by increasing temperature and/or flow rates were captured, demonstrating the ability to use these gratings in methanol steam reforming. Similar experimental work was conducted to validate the possibility of using fiber Bragg gratings as temperature sensors in methane reforming. Using a regenerated grating array, data was collected for 13 operating conditions. The conclusions arising from this work are similar to those drawn from the methanol steam reforming work. The regenerated FBGs exhibited a behaviour that has not been reported in the literature which is referred to in this thesis as secondary erasure. This behaviour caused some instability in the grating signal and erroneous readings for some operating conditions. Despite this, the grating measurements captured the zones of low temperatures in the reformer and the small changes brought about by increasing the reforming temperature and lowering the steam to carbon ratio. / Graduate

In this work the performance of cerium-based oxygen carriers is investigated in a simulated chemical looping dry reforming system using methane and carbon dioxide as fuel and oxidizing gas respectively. The samples to be studied are pure cerium oxide and cerium oxide doped with zirconium, yttrium, samarium, and scandium more specifically: CeO2, Ce0.8Y0.2O1.9, Ce0.85Y0.05Zr0.1O1.975, Ce0.95Zr0.05O2, Ce0.9Sm0.05Zr0.05O1.975, and Ce0.9Sc0.05Zr0.05O1.975. Characteristics such as crystallography including lattice parameter and particle size of the samples are evaluated using X-ray diffraction (XRD) and particle size analysis. The oxygen transport capacity will also be measured using a thermogravimetric analyzer (TGA). This method of measurement also allowed for insight on oxygen release temperatures as well as recyclability of the samples. The particle size analysis showed that the synthesis method of precipitation-agglomeration resulted in samples with consistent particle size distribution indicating the method can be scaled up. The X-ray analysis of samples before and after the TGA tests show that all the materials tested had a cubic fluorite crystal structure which was maintained through the oxidation reduction cycles. The lattice parameter was found to increase slightly with a loss in oxygen content in the samples. The addition of trivalent dopants resulted in a decrease in the temperature of initiation of reduction in methane. While reduction of commercial ceria initiated near 800 oC. the addition of trivalent dopants resulted in a lowering of the initialization temperature between of 150 – 200oC. The activation energy of commercial ceria was 248.42 kJ/mol for reduction in methane, indicating that the rate controlling mechanism is chemical reaction rather than diffusion. The addition of trivalent dopants resulted in a significant lowering in the activation energy. The activation energies obtained in this study show that the addition of dopant increased the significance of diffusion through the solid and the controlling mechanisms were both diffusion and chemical reaction. Overall, the addition of trivalent dopants enhanced the extent of oxygen exchange in CLDR process.

This thesis reports the outcome of a simulation study that examines the feasibility of using hydrogen peroxide as an alternative oxidant in the autothermal reforming (ATR) of diesel. The primary objective is to compare hydrogen peroxide's performance against conventional oxidants in reforming, focusing on product distribution and three pivotal process properties: diesel conversion, hydrogen production, and ethylene generation. The study further investigates the influence of the heat of decomposition on the performance and reaction routes of different oxidants. Additionally, a comparative analysis is conducted on the reforming performance in different reformer configurations, specifically contrasting a combined-reformer-configuration with a catalytic-reformer configuration. The ANSYS Chemkin-Pro is utilized to understand the potential benefits and challenges of the proposed approached. A reduced chemical mechanism of N-heptane/Toluene reforming as a surrogate for diesel, combined with a detailed surface reaction mechanism of propene on a three-way Pt/Rh catalyst are used in this study. It is found that the use of hydrogen peroxide as an oxidant demonstrated a complete fuel conversion and 183% higher hydrogen yield when compared with conventional oxidants. It also led to a 12% lower generation of ethylene, a precursor for coke formation. The catalytic-reformer configuration showed superior performance over the combined-reformer-configuration in terms of hydrogen yield. The insights from this study offer valuable perspectives on the feasibility and efficiency of using hydrogen peroxide as an alternative oxidant in the ATR of diesel, paving the way for potential advancements in the field.

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